Shape memory crosslinked polyurethanes containing thermoreversible Diels‐Alder couplings

Crosslinked polyurethanes (PUs) containing irreversible (allophanate) and reversible Diels‐Alder chemical bonds were synthesized using various diisocyanates (methylene diphenyl diisocyanate MDI, 1,6‐hexamethylenediisocyanate HDI) and poly(?‐caprolactone) ((PCL) with different molecular weights (M_n = 10 kg/mol, 25 kg/mol, 50 kg/mol) as diol component. The melting/crystallization of PCL and the reversible DA bonds acted as temperature‐activated switches for shape memory performances, while allophanate network provided the permanent crosslinks for these PUs. The reversible DA bonds were obtained by the reaction of diisocyanate‐ended prepolymers with furfurylamine (FA) followed by the addition of bismaleimide (BMI). The permanent crosslinks between the linear chains containing DA bonds were achieved using additional amounts of diisocyanates (MDI or HDI). The above reaction path was supported by infrared spectroscopic results and swelling experiments. Tensile mechanical and shape memory properties in tension of the PUs were determined and discussed as a function of composition and crosslink densities deduced from swelling and dynamic mechanical analysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44145.     

Sustained release of potassium diclofenac from a pH‐responsive hydrogel based on gum arabic conjugates into simulated intestinal fluid

This work describes the preparation, the swelling properties and the potassium diclofenac (KDF) release profile of hydrogels of gum arabic (GA), N′,N′‐dimethylacrylamide, and methacrylic acid. In order to convert GA into a hydrogel, the polysaccharide was vinyl‐modified with glycidyl methacrylate. The hydrogels showed pH‐responsive swelling changes, which were more expressive in the basic environment. Release data of KDF were adjusted to a diffusion‐based kinetic model that provides an important insight on affinity of the drug for hydrogel and solvent, which may be the leading parameter for release of guest molecules from polymers. The KDF release from the hydrogels into simulated intestinal fluid decreases when the amount of modified GA increases. This was demonstrated to be due to the higher affinity of KDF for GA‐richer hydrogel, which makes the anti‐inflammatory release less favorable. The analysis of released drug half‐time (t_1/2 = 16.10 and 21.51 h) indicated sustained release characteristics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43319.     

Utilization of ramon seeds (Brosimum alicastrum swarts) as a new source material for thermoplastic starch production

The development and characterization of biodegradable polymers deriving from renewable natural sources has attracted much attention. The aim of this work was to partially characterize a thermoplastic starch obtained from the starch of seeds from the ramon tree (TPS‐RS) as an option to substitute thermoplastic starch from corn (TPS‐CS), in some of its applications. At 55% of relative humidity (RH), TPS‐RS had higher tensile strength and deformation than TPS‐CS. X‐ray diffraction analysis showed similar values in residual crystallinity (percentage of crystallinity that remains after plasticization process) in both TPS. The SEM micrographs showed a few remnant granular structures in the TPS‐RS. The FTIR showed a greater intensity in band at 1016 cm^?1 in the TPS‐CS and TPS‐RS in comparison with their corresponding native starch, indicating an increase in the amorphous region after plasticization. The TGA analysis showed greater thermal stability in TPS‐CS (340 °C) compared with TPS‐RS (327 °C). In addition, the glass transition temperature in both TPS was 24 °C. The results obtained represent a starting point to potentialize the use of TPS‐RS instead of TPS‐CS for the development of new biodegradable materials for practical applications in different areas. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44235.     

Increased HDL Size and Enhanced Apo A-I Catabolic Rates Are Associated With Doxorubicin-Induced Proteinuria in New Zealand White Rabbits

The catabolism and structure of high‐density lipoproteins (HDL) may be the determining factor of their atheroprotective properties. To better understand the role of the kidney in HDL catabolism, here we characterized HDL subclasses and the catabolic rates of apo A‐I in a rabbit model of proteinuria. Proteinuria was induced by intravenous administration of doxorubicin in New Zealand white rabbits (n = 10). HDL size and HDL subclass lipids were assessed by electrophoresis of the isolated lipoproteins. The catabolic rate of HDL‐apo A‐I was evaluated by exogenous radiolabelling with iodine‐131. Doxorubicin induced significant proteinuria after 4 weeks (4.47 ± 0.55 vs. 0.30 ± 0.02 g/L of protein in urine, P < 0.001) associated with increased uremia, creatininemia, and cardiotoxicity. Large HDL2b augmented significantly during proteinuria, whereas small HDL3b and HDL3c decreased compared to basal conditions. HDL2b, HDL2a, and HDL3a subclasses were enriched with triacylglycerols in proteinuric animals as determined by the triacylglycerol‐to‐phospholipid ratio; the cholesterol content in HDL subclasses remained unchanged. The fractional catabolic rate (FCR) of [¹³¹I]‐apo A‐I in the proteinuric rabbits was faster (FCR = 0.036 h^?1) compared to control rabbits group (FCR = 0.026 h^?1, P < 0.05). Apo E increased and apo A‐I decreased in HDL, whereas PON‐1 activity increased in proteinuric rabbits. Proteinuria was associated with an increased number of large HDL2b particles and a decreased number of small HDL3b and 3c. Proteinuria was also connected to an alteration in HDL subclass lipids, apolipoprotein content of HDL, high paraoxonase‐1 activity, and a rise in the fractional catabolic rate of the [¹³¹I]‐apo A‐I.     

Toward the prediction of porous membrane permeability from morphological data

One of the challenges in membrane technology is predicting permeability in porous membranes for liquid applications in an easy and inexpensive way. This is the aim of this work. To achieve this objective, several techniques can be considered. In this study, a morphological approach from two‐dimensional scanning electron micrographs is proposed. First, numerical membrane morphological parameters have been determined from micrographs by using the QUANTS tool, which applies a texture recognition process. Second, the obtained data have been fit to the Darcy's and Hagen–Poiseuille models to calculate permeations. The QUANTS results have also been compared with the ones obtained through a mercury porosimeter, which is a classic and well‐known methodology. Each parameter of the Hagen–Poiseuille model has been analyzed. A comparison between experimentally measured permeations and calculated ones has been performed. An even easier approach is proposed to predict flow rate with the only knowledge of membrane surface mean pore size. This method is based on cross‐section pore size interpolation by using function fits from surface mean pore sizes. The obtained results show a reasonable agreement between measured and computed results, making this technique a valid approach for predicting membrane permeability. POLYM. ENG. SCI., 56:118–124, 2016. © 2015 Society of Plastics Engineers     

Platelet lysate and adipose mesenchymal stromal cells on silk fibroin nonwoven mats for wound healing

In this work platelet lysate (PL) and adipose‐derived mesenchymal stromal cells (ASCs) seeded on nonwoven fibroin mats were in vitro and in vivo evaluated for tissue regenerative applications. Nonwoven mats obtained by a large scale water entanglement technique were characterized for their physico‐chemical properties. Results indicated a high purity of fibroin fibers, their stability after sterilization process and appropriate technological properties suitable for tissue engineering. Moreover, the scaffolds in vitro supported adhesion and migration of ASCs and the presence of PL improved the cell proliferation. The products were then applied on epithelial/dermal wounds carried out on the dorsal surface of rabbit: the skin reparative process was solved in 9 days, with a completely restitutio ad integrum of the epithelium in animals treated with PL alone; ASCs did not further improve the wound healing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42942.     

Acrylic bone cements modified with poly(ethylene glycol)‐based biocompatible phase‐change materials

The high polymerization temperature of acrylic bone cements used in hip replacement implantation may cause thermal necrosis of surrounding tissues. In order to reduce the polymerization temperature, acrylic bone cement has been modified with a biocompatible polymeric phase‐change material (PCM) based on poly(ethylene glycol) (PEG) of different molecular weights and stabilized with potato starch. Structural and morphological studies were performed, and the thermal and mechanical properties were investigated. The incorporation of PEG‐based PCM led to a decrease in the polymerization temperature of bone cement from 70 °C for unmodified cement to 58 °C for modified cement. Modified cement materials were stable in incubation tests, although acoustic analysis data revealed a decrease in propagation speed after incubation, which indicates formation of material defects (pores, cracks, voids, etc.) due to water activity. However, in the regeneration process, these defects can be filled by freshly grown bone tissue leading to better incorporation of bone cement replacements into tissue. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43898.     

Solvent and relative humidity effect on highly ordered polystyrene honeycomb patterns analyzed by Voronoi tesselation

Highly ordered honeycomb‐patterned polystyrene surfaces are efficiently prepared by static breath figure method. The structured arrays can be obtained by casting a dilute solution polymer on glass substrates under various conditions. Tetrahydrofuran and chloroform are used as solvent to form cavities of several micrometers. The analysis of the surfaces indicates nonlinear relation between concentration and pore size in this system. Voronoi tessellations of the polystyrene surfaces at different relative humidity (RH) are achieved, and each conformational entropy determined. Optimum parameters of concentration and RH are obtained for both solvents. Analysis of hole size distribution and conformational entropy demonstrates the high order of the films obtained. This is a promising method for the fabrication of homogeneous and highly porous films from polystyrene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44004.     

Effect of CO2 Exposure on the Chemical Stability and Mechanical Properties of BaZrO3‐Ceramics

The reactivity of BaZrO₃ with CO₂ has been addressed as one of the major challenges with BaZrO₃‐based electrolytes in protonic ceramic fuel cells. Here, we present a study of the effect of CO₂ exposure on BaZrO₃‐materials at elevated temperatures. Dense BaZr_1?xY_xO_3?x/2 (x = 0, 0.05, 0.1, 0.2) and BaCe_0.2Zr_0.7Y_0.1O_2.95 ceramics were prepared by sintering of powder prepared by spray pyrolysis. The Vickers indentation method was used to determine the hardness and estimate the fracture toughness of pristine materials as well as the corresponding materials exposed to CO₂. Formation of BaCO₃ on the surface of exposed ceramics was confirmed by X‐ray diffraction and electron microcopy. The reaction resulted in formation of Ba‐deficient perovskite at the exposed surface. The reaction with CO₂ was most pronounced at 650°C compared to the other temperatures applied in the study. The reactivity was also shown to depend on the Y‐content and the grain size and was most pronounced for BaZr_0.9Y_0.1O_2.95. The reaction with CO₂ was observed to have a profound effect on the fracture toughness of the ceramics, demonstrating a depression of the mechanical stability of the materials. The results are discussed with respect to the chemical and mechanical stability of BaZrO₃ materials, with particular emphasis on the composition and grain size.